Heterocyclic compounds

ABSTRACT

Compounds of the formula    &lt;IMAGE&gt;  I  where B is oxygen, sulfur, imino or &gt;N-R1, the ring A may be substituted, and R, Y1 to Y4 and Z are conventional dye substituents. The compounds according to the invention give brilliant, very fast dyeings on polyesters and mass-colorations of plastics.

The present invention provides novel heterocyclic compounds which in one of the possible tautomeric forms correspond to the general formula I ##STR2##

where B is oxygen, sulfur, NH or ##STR3##

R is C₁ -C₈ -alkyl which may or may not be interrupted by oxygen and is unsubstituted or substituted by hydroxyl, phenoxy, cyano, C₁ -C₄ -alkoxycarbonyl, hydroxycarbonyl, C₁ -C₄ -alkanoyloxy, unsubstituted or N-substituted carbamoyl or phenyl, or is phenyl which is unsubstituted or substituted by chlorine, bromine, methyl, ethyl, methoxy or ethoxy, or is C₁ -C₄ -alkoxycarbonyl or cyano, or is unsubstituted or N-substituted carbamoyl, or, if B is sulfur, NH or --N--R¹, ##STR4## may also be hydrogen,

R¹ is C₁ -C₄ -alkyl or benzyl,

Y¹ is hydrogen, chlorine, bromine, C₁ -C₄ -alkyl, methoxy, ethoxy, phenoxy, phenyl, nitro or SO₂ T, where

T is hydroxyl or C₁ -C₄ -alkoxy, or is phenoxy which is unsubstituted or substituted by chlorine, bromine, C₁ -C₄ -alkyl, methoxy or ethoxy, or is substituted or unsubstituted amino or is unsubstituted or substituted alkyl or aryl,

Y² hydrogen, chlorine, bromine, C₁ -C₄ -alkyl, methoxy or ethoxy,

or Y¹ and Y² together are a fused benzo ring,

Y³ is hydrogen, chlorine, bromine, C₁ -C₄ -alkyl, hydroxyl, methoxy or ethoxy,

Y⁴ is hydrogen, chlorine, bromine, C₁ -C₄ -alkyl, methoxy, ethoxy, hydroxyl, phenoxy or phenyl, or

Y³ and Y⁴ together are a fused benzo ring and

Z is hydroxyl, amino or --NHR¹, and

the ring A may additionally be monosubstituted or polysubstituted by chlorine, bromine, nitro, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, phenoxy, amino, C₁ -C₄ -alkylamino, di-C₁ -C₄ -alkylamino, acylamino or phenyl.

Specific examples of radicals R are CH₃, C₂ H₅, C₃ H₇, C₄ H₉, C₅ H₁₁, C₆ H₁₃, C₈ H₁₇, ##STR5## CH₂ CHOHCH₃, (CH₂)₄ OH, (CH₂)₆ OH, C₂ H₄ OCH₃, C₂ H₄ OC₂ H₅, C₂ H₄ OC₄ H₉, ##STR6## (CH₂)₃ OC₂ H₄ OCH₃, (CH₂)₃ OC₂ H₄ OC₂ H₅, (CH₂)₃ OC₂ H₄ OC₄ H₉, (CH₂)₃ OC₂ H₄ OC₆ H₅, C₂ H₄ CN, C₂ H₄ COOCH₃, C₂ H₄ COOC₂ H₅, C₂ H₄ COOC₄ H₉, CH₂ COOCH₃, CH₂ COOC₂ H₅, CH₂ COOC₄ H₉, CH₂ COOH, C₂ H₄ OCOCH₃, C₂ H₄ OCOC₂ H₅, C₂ H₄ CONHCH₃, C₂ H₄ CONHC₂ H₅, C₂ H₄ CONHC₃ H₇, C₂ H₄ C₆ H₅, C₆ H₅, C₆ H₄ Cl, C₆ H₄ CH₃, COOCH₃, COOC₂ H₅, COOC₃ H₇, COOC₄ H₉, CONHCH₃, CONHC₂ H₅, CONHC₄ H.sub. 9 and CONC₆ H₅.

Specific examples of radicals SO₂ T are SO₃ H, SO₃ CH₃, SO₃ C₄ H₉, SO₃ C₆ H₅, SO₃ C₆ H₄ CH₃, SO₃ C₄ H₄ Cl, SO₃ C₆ H₄ C₂ H₅, SO₃ C₆ H₃ (CH₃)₂, SO₃ C₆ H₃ Cl₂, SO₃ C₆ H₄ OCH₃, SO₂ NH₂, SO₂ NHCH₃, SO₂ NHC₂ H₅, SO₂ NHC₃ H₇, SO₂ NHC₄ H₉, SO₂ NHC₆ H₁₃, SO₂ N(C₂ H₅), SO₂ N(C₄ H₉)₂, SO₂ NHCHCH₂ OCH₃, SO₂ NHC₂ H₄ OC₂ H₅, SO₂ NH(CH₂)₃ OC₂ H₅, SO₂ NH(CH₂)₃ N(CH₃)₂, SO₂ NH(CH₂)₃ N(C₄ H₉)₂, SO₂ NHC₂ H₄ N(CH₃)₂, SO₂ NHC₆ H₅, SO₂ CH₃, SO₂ C₂ H₅, SO₂ C₄ H₉, SO₂ C₆ H₅, SO₂ C₆ H₄ CH₃, SO₂ CH₂ CH₂ OH, SO₂ CH₂ CH₂ OCH₃, SO₂ CH₂ CH₂ N(CH₃)₂, ##STR7##

Acylamino radicals which may be present in the ring A are formylamino, acetylamino, propionylamino, benzoylamino, chlorobenzoylamino, methylbenzoylamino and methylchlorobenzoylamino.

A compound of the formula I may be prepared by

(a) condensing a compound of the formula ##STR8## with a compound of the formula ##STR9## or

(b) condensing a compound of the formula ##STR10## with a compound of the formula ##STR11##

The reactions are known in principle. Details may be found in the Examples, where parts and percentages are by weight, unless stated otherwise.

Compounds of particular importance are those of the formula I a ##STR12## where B, R, Y², Y³ and Z have the above meanings and the ring A may be substituted by methyl, ethyl, methoxy or ethoxy.

Preferably, B is oxygen, Y² is hydrogen, chlorine, methyl, methoxy or ethoxy, Y³ is hydrogen, chlorine or methyl, Z is hydroxyl and R is --CH₃, --C₂ H₅, --C₃ H₇ or --C₄ H₉.

The compounds of the formula I are yellow to red and are suitable as dyes for dyeing textiles consisting of natural or synthetic fibers, especially polyesters. The dyeings obtained have excellent fastness characteristics, amongst which the lightfastness, fastness to thermofixing and wetfastness may be singled out.

Some of the dyes are also suitable for the mass coloring of thermoplastics and some for the process described in German Patent 1,811,796.

EXAMPLE 1

6.9 parts of 1-imino-3-(4'-hydroxycoumarin-3'-yl)isoindoline and 4.3 parts of 1-methyl-2-cyanomethylbenzimidazole in 50 parts by volume of glacial acetic acid are heated very rapidly to the reflux temperature and stirred thereat for 30 minutes. The reaction mixture is then cooled and the dye which has precipitated is filtered off and washed with methanol. 6.5 parts of the dye of the formula ##STR13## are obtained, having a melting point of 265°-267° C.

EXAMPLE 2

3.9 parts of the monocondensation product of 1,3-diimino-isoindoline and 1-methyl-2-cyanomethyl-benzimidazole are stirred with 2.1 parts of 4-hydroxycoumarin in 30 parts by volume of acetic acid and 10 parts by volume of acetic anhydride for 30 minutes at 100° C. The reaction mixture is cooled and the dye which has precipitated is filtered off and washed with methanol. 4.5 parts of a compound which is identical with the dye from Example 1 and has a melting point of 270°-274° C. are obtained.

EXAMPLE 3

4.8 parts of 1-methyl-2-cyanomethyl-benzimidazole are added to 5.8 parts of 1,3-diiminoisoindoline in 30 parts by volume of dimethylformamide at room temperature. The reaction mixture is then stirred for 4 hours at room temperature. Thereafter, 4.5 parts of 4-hydroxycoumarin and 3 parts by volume of acetic anhydride are added and the reaction mixture is heated at 100° C. After 30 minutes, it is cooled and the dye which has precipitated is filtered off and washed with methanol. 9.9 parts of a dye which is identical with the dye from Example 1 and has a melting point of 268°-273° C. are obtained.

The Table which follows lists further dyes of the formula ##STR14## which are obtained from the corresponding starting materials by following a method similar to Example 1, 2 or 3.

    __________________________________________________________________________     Ex-                                     Melting                                                                             Hue on                            ample                                                                              Y.sup.1                                                                           Y.sup.2                                                                          Y.sup.3                                                                           Y.sup.4                                                                           A      B    Z     R      range °C.                                                                    polyester                         __________________________________________________________________________     4   CH.sub.3                                                                          H H  H  unsubstituted                                                                         O    OH    CH.sub.3                                                                              268-72                                                                              red                               5   CH.sub.3                                                                          H H  H  "      O    OH    C.sub.2 H.sub.5                                                                       213-218                                                                             red                               6   H  H H  H  "      O    OH    C.sub.2 H.sub.5                                                                       310-320                                                                             red                               7   H  H H  H  "      O    NH.sub.2                                                                             CH.sub.3                                                                              242-244                                                                             yellow                            8   H  H H  H  "      O    NHC.sub.4 H.sub.9                                                                    CH.sub.3                                                                              245-248                                                                             yellow                            9   H  H CH.sub.3                                                                          H  "      O    OH    C.sub.2 H.sub.5                                                                       290-295                                                                             red                               10  H  H H  H  "      O    OH    CH.sub.2C.sub.6 H.sub.5                                                               255-262                                                                             red                               11  H  H H  H  "      O    OH    n-Hexyl                                                                               198-201                                                                             red                               12  Cl Cl                                                                               H  H  "      O    OH    C.sub.2 H.sub.5                                                                       290-292                                                                             red                               13  H  H H  H  "      O    OH                                                                                    ##STR15##                                                                            255-260                                                                             red                               14  H  H H  H  "      O    OH                                                                                    ##STR16##                                                                            240-245                                                                             red                               15  H  H H  H  "      O    OH    C.sub.3 H.sub.7n                                                                      230-235                                                                             red                               16  H  H H  H  "      O    OH    n-C.sub.4 H.sub.9                                                                     225-230                                                                             red                               17  CH.sub.3                                                                          H H  H  "      O    OH    n-C.sub.3 H.sub.7                                                                     195-198                                                                             red                               18  H  H CH.sub.3                                                                          H  "      O    OH    CH.sub.3                                                                              219-224                                                                             red                               19  H  H H  H  "      NH   OH    CH.sub.3                                                                              >320 red                               20  H  H H  H  "      NCH.sub.3                                                                           OH    CH.sub.3                                                                              215-224                                                                             red                               21  CH.sub.3                                                                          H H  H  "      NH   OH    CH.sub.3                                                                              285-295                                                                             red                               22  CH.sub.3                                                                          H H  H  "      NH   OH    C.sub.2 H.sub.5                                                                       290-295                                                                             red                               23  H  H H  H  "      NCH.sub.3                                                                           OH    C.sub.2 H.sub.5                                                                       200-205                                                                             red                               24  Cl Cl                                                                               H  H  "      "    OH    CH.sub.3                                                                              230-235                                                                             red                               25  Cl Cl                                                                               H  H  "      NH   OH    C.sub.2 H.sub.5                                                                       280-285                                                                             red                               26  H  H                                                                                 ##STR17##                                                                           "      O    OH    CH.sub.3                                                                              >300 red                               27  H  H "     "      O    OH    C.sub.2 H.sub.5                                                                       >300 red                               28  Cl H Cl H  "      O    OH    CH.sub.3                                                                              290-295                                                                             red                               29  H  H H  H  "      S    OH    H           red                               30  H  H H  H  "      S    OH    CH.sub.3    red                               31  H  H H  H  "      S    OH    C.sub.2 H.sub.5                                                                            red                               __________________________________________________________________________ 

We claim:
 1. A heterocyclic compound which in one of the possible tautomeric forms corresponds to the formula (I): ##STR18## where (a) B is oxygen, sulfur, NH or ##STR19## (b) R is C₁ -C₈ -alkyl which may or may not be interrupted by oxygen and is unsubstituted or substituted by hydroxyl, phenoxy, cyano, C₁ -C₄ -alkoxycarbonyl, hydroxycarbonyl, C₁ -C₄ -alkanoyloxy, --CONH₂, --CONHCH₃, --CONHC₂ H₅, --CONHC₃ H₇ or phenyl; oris phenyl which is unsubstituted or substituted by chlorine, bromine, methyl, ethyl, methoxy or ethoxy; or is C₁ -C₄ -alkoxycarbonyl or cyano; or is --CONH₂, CONHCH₃, --CONHC₂ H₅, --CONHC₄ H₉ or CONHC₆ H₅ ; or if B is sulfur, NH or ##STR20## may also be hydrogen, (c) R¹ is C₁ -C₄ -alkyl or benzyl; (d) Y¹ is hydrogen, chlorine, bromine, C₁ -C₄ -alkyl, methoxy, ethoxy, phenoxy, phenyl, nitro or SO₂ T; (e) T is hydroxyl or C₁ -C₄ -alkoxy; or is phenoxy which is unsubstituted or substituted by chlorine, bromine, C₁ -C₄ -alkyl, methoxy or ethoxy; or is NH₂, NHCH₃, NHC₂ H₅, NHC₃ H₇, NHC₄ H₉, NHC₆ H₁₃, N(C₂ H₅)₂, N(C₄ H₉)₂, NHCHCH₂ OCH₃, NHC₂ H₄ OC₂ H₅, NH(CH₂)₃ OC₂ H₅, NH(CH₂)₃ N(CH₃)₂, NH(CH₂)₃ N(C₄ H₉)₂, NHC₂ H₄ N(CH₃)₂, NHC₆ H₅, CH₃, C₂ H₅, C₄ H₉, C₆ H₅, C₆ H₄ CH₃, CH₂ CH₂ OH, CH₂ CH₂ OCH₃, CH₂ CH₂ N(CH₃)₂, CH₂ CH(OH)CH₂ Cl or CH₂ CH(OH)CH₂ OH; (f) Y² is hydrogen, chlorine, bromine, C₁ -C₄ -alkyl, methoxy or ethoxy; (g) Y³ is hydrogen, chlorine, bromine, C₁ -C₄ -alkyl, hydroxyl, methoxy or ethoxy, (h) Y⁴ hydrogen, chlorine, bromine, C₁ -C₄ -alkyl, methoxy, ethoxy, hydroxyl, phenoxy, phenyl, or Y³ and Y⁴ together are a fused benzo ring; (i) Z is hydroxyl, amino or --NHR¹ ; and the ring A may additionally be monosubstituted or polysubstituted by chlorine, bromine, nitro, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, phenoxy, amino, C₁ -C₄ -alkylamino, di-C₁ -C₄ -alkylamino, formylamino, acetylamino, propionylamino, benzoylamino, chlorobenzoylamino, methylbenzoylamino, methylchlorobenzoylamino or phenyl.
 2. The compound as claimed in claim 1 of the formula (Ia) ##STR21## where B,R,Y²,Y³ and Z have the meanings given in claim 1 and wherein the ring A is substituted by methyl, ethyl, methoxy or ethoxy. 